CN103063725A - Solid ammonium ion electrode based on conductive polyaniline and preparing method thereof - Google Patents
Solid ammonium ion electrode based on conductive polyaniline and preparing method thereof Download PDFInfo
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- CN103063725A CN103063725A CN2012105381496A CN201210538149A CN103063725A CN 103063725 A CN103063725 A CN 103063725A CN 2012105381496 A CN2012105381496 A CN 2012105381496A CN 201210538149 A CN201210538149 A CN 201210538149A CN 103063725 A CN103063725 A CN 103063725A
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Abstract
The invention discloses a solid ammonium ion electrode based on conductive polyaniline and a preparing method thereof. The solid ammonium ion electrode comprises a metal wire, the conductive polyaniline, soluble conductive polyaniline, ammonium ion sensitive film and a heat shrink tube, wherein a layer of the conductive polyaniline is electroplated on the surface of the lower portion of the metal wire, a layer of the soluble conductive polyaniline is wrapped on the outer surface of the conductive polyaniline, the ammonium ion sensitive film is wrapped on the outer surface of the soluble conductive polyaniline, and the heat shrink tube is wrapped on a portion located in the middle of the metal wire and with a distance greater than 0.5-1cm from the end portion of the ammonium ion sensitive film. The solid ammonium ion electrode based on the conductive polyaniline has the advantages of being high in mechanical strength, large in toughness, high in sensitivity, small in size, quick in detection response, low in detection limit, long in service life and the like. When matched with a solid reference electrode for use, the solid ammonium ion electrode based on the conductive polyaniline is applicable to on line detection and long-term in situ monitoring of ammonium ion content in seawater, aquaculture water and chemistry or chemical industry water mediums.
Description
Technical field
The present invention relates to the electrochemical detection technology, relate in particular to a kind of solid ammonium ion electrode based on electrically conductive polyaniline and preparation method thereof.
Background technology
Ammonium ion content is the important parameter that carries out environmental evaluation in the water body, and for the activity of understanding organism in water, microorganism, and environmental pollution monitoring is significant.The commercial ammonium ion electrode that is used at present this type of purpose all belongs to liquid membrane electrode, and namely electrode interior need to fill electrolyte solution, i.e. and so-called " salt bridge ", its effect is the response signal that conduction detects between ion sensitive membrane and plain conductor.The major defect of liquid film type electrode comprises: volume more greatly, fragile, easily signal drift occurs, serviceable life is short.
Compare with traditional liquid film type electrode, solid electrode has that volume is little, intensity is high, and the comprehensive advantages such as long service life are suitable for natural water body, especially the long term monitoring of marine environment and online observation.The present invention is directed to this demand and proposed a kind of solid ammonium ion electrode based on electrically conductive polyaniline and preparation method thereof.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of solid ammonium ion electrode based on electrically conductive polyaniline and preparation method thereof is provided.
The objective of the invention is to be achieved through the following technical solutions:
Solid ammonium ion electrode based on electrically conductive polyaniline comprises tinsel, electrically conductive polyaniline, fusible conductive polyaniline, ammonium ion sensitive membrane, heat-shrink tube, the tinsel lower surface is electroplated one deck electrically conductive polyaniline, outside surface at electrically conductive polyaniline coats one deck fusible conductive polyaniline, outside surface at fusible conductive polyaniline is coated with again the ammonium ion sensitive membrane, is coated with heat-shrink tube in the middle part of the tinsel and be 0.5～1 centimetre away from ammonium ion sensitive membrane end more than outside the part.
Described tinsel is Ag, Au, Pt, or the surface is coated with copper wire or the nickel wire of Ag, Au, Pt metal film.Described fusible conductive polyaniline be tinsel in the hydrochloric acid solution of aniline monomer, electroplate to form.Described fusible conductive polyaniline is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.
Step based on the preparation method of the solid ammonium ion electrode of electrically conductive polyaniline is as follows:
1) with length be 5～15 centimetres tinsel, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1～2M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) aniline and hydrochloric acid are mixed with the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, perhaps with the aniline hydrochloride chip solid, are dissolved in without in the ammonium water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline with cyclic voltammetry on top layer wiry by the CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline, the dinethylformamide saturated solution is inserted in the crucible that fills sand, dries 4～6 hours in 80～150 ℃ of baking ovens;
4) the ammonium ion carrier A mmonium Ionophore I of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in the DMF, are mixed with mixed solution, its composition is respectively by percentage to the quality:
Form A:
Ammonium ion carrier I 6.9%;
Four (4-chlorphenyl) potassium borate 0.7%;
2-nitrobenzene octyl ether 92.4%;
Form B:
Ammonium ion carrier I 0.2%;
2-nitrobenzene octyl ether 69.00%;
PVC 30.80% ；
Form C:
Ammonium ion carrier I 1.00%;
Di-n-octyl sebacate 66.80%;
PVC 32.20% ；
5) dip mixed solution 1～3 time with the surperficial electrode that is coated with soluble polyaniline, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains the ammonium ion sensitive membrane after volatilizing fully;
6) heat-shrink tube is coated on tinsel middle part and be part 0.5～1 centimetre away from ammonium ion sensitive membrane end more than.
Exploring electrode volume of the present invention is little, highly sensitive, and probe response is fast, has very high physical strength and toughness, has good serviceability under condition of high voltage.Therefore be applicable to the ammonium ion content in seawater, breeding water and chemistry, the chemical industry aqueous medium is surveyed and long-term in-situ monitoring online, compare with traditional sampling analysis, both alleviated working strength, avoided the secondary pollution in the sampling process, improved again the real-time of data, reliability.
Description of drawings
Fig. 1 is based on the structural representation of the solid ammonium ion electrode of electrically conductive polyaniline;
Among the figure: tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, ammonium ion sensitive membrane 4, heat-shrink tube 5.
Embodiment
Solid ammonium ion electrode based on electrically conductive polyaniline comprises tinsel 1, electrically conductive polyaniline 2, fusible conductive polyaniline 3, ammonium ion sensitive membrane 4, heat-shrink tube 5, tinsel 1 lower surface is electroplated one deck electrically conductive polyaniline 2, outside surface at electrically conductive polyaniline 2 coats one deck fusible conductive polyaniline 3, outside surface at fusible conductive polyaniline 3 is coated with again ammonium ion sensitive membrane 4, tinsel 1 middle part and be 0.5～1 centimetre away from ammonium ion sensitive membrane 4 ends more than the part outside be coated with heat-shrink tube 5.
Described tinsel 1 is Ag, Au, Pt, and its effect is that electrode surface is passed to detection circuit by the response signal that the ammonium ion carrier forms.The recommendation noble metal, the undesired signal that can avoid the dissolved constituent in tinsel self and the water body to form because of electrochemical reaction.Be to reduce cost, can use the surface to be coated with the copper wire, nickel wire of Ag, Au, Pt as electrode base material.
Described electrically conductive polyaniline 2 be tinsel 1 in the hydrochloric acid solution of aniline monomer, electroplate to form.Conductive polyaniline film 2 has good electric conductivity, and there is not obvious interlayer barrier in the electric current conduction between the two; In addition, conductive polyaniline film has changed surface nature wiry, has increased the affinity between the organic coating layer of it and follow-up formation.
Described fusible conductive polyaniline 3 is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.The doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline can use commercial product, also can oneself be synthetic, and its chemical synthesis process is consistent with polyaniline, is the mixture replacing aniline of aniline and 2,5-dimethoxyaniline being pressed 5:1 to 1:5.
Use the doped hydrochloride multipolymer of aniline and 2,5-dimethoxyaniline to have triple effects:
It has electric conductivity as electrically conductive polyaniline;
The plated conductive polyaniline composition of it and internal layer approaches, and chemical affinity is strong;
It and outermost layer ammonium ion carrier can both be dissolved in DMF, thereby can be partly dissolved in the process that coats the ammonium ion carrier, make ammonium ion sensitive membrane and soluble polyaniline close contact, conductive impairment between eliminating layer.
Step based on the preparation method of the solid ammonium ion electrode of electrically conductive polyaniline is as follows:
1) with length be 5～15 centimetres tinsel 1, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1～2M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) aniline and hydrochloric acid are mixed with the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, perhaps with the aniline hydrochloride chip solid, are dissolved in without in the ammonium water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline 2 with cyclic voltammetry on the top layer of tinsel 1 by the CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel 1 is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline 2, the dinethylformamide saturated solution is inserted in the crucible that fills sand, dries 4～6 hours in 80～150 ℃ of baking ovens;
4) the ammonium ion carrier A mmonium Ionophore I of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in the DMF, are mixed with mixed solution, its composition is respectively by percentage to the quality:
Form A:
Ammonium ion carrier I 6.9%;
Four (4-chlorphenyl) potassium borate 0.7%;
2-nitrobenzene octyl ether 92.4%;
Form B:
Ammonium ion carrier I 0.2%;
2-nitrobenzene octyl ether 69.00%;
PVC 30.80% ；
Form C:
Ammonium ion carrier I 1.00%;
Di-n-octyl sebacate 66.80%;
PVC 32.20% ；
5) dip mixed solution 1～3 time with the surperficial electrode that is coated with soluble polyaniline 3, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane 4 after volatilizing fully; Vacuum drying under the recommendation normal temperature avoids using hyperthermia drying, is in order better to protect the activity of ammonium ion sensitive membrane;
6) heat-shrink tube 5 is coated on tinsel 1 middle part and be part 0.5～1 centimetre away from ammonium ion sensitive membrane 4 ends more than.
1) with length be 10 centimetres tinsel 1, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) take by weighing 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml without in the ammonium water, make the aniline hydrochloride solution of 1M; Electroplate one deck electrically conductive polyaniline 2 with cyclic voltammetry on the top layer of tinsel 1 by the CHI760D electrochemical workstation;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel 1 is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) take by weighing 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 5:1), be dissolved in and be mixed with saturated solution among the 10mlDMF, the electrode that is coated with electrically conductive polyaniline 2 with the surface dips rapidly the N of soluble polyaniline, dinethylformamide (DMF) saturated solution, be inserted in the crucible that fills sand, oven dry is 4 hours in 150 ℃ of baking ovens;
4) ammonium ion carrier and attached component thereof are dissolved among the DMF according to forming A, are mixed with mixed solution, its composition A is by percentage to the quality:
Ammonium ion carrier (Ammonium ionophore I) 6.9%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.7%,
2-nitrobenzene octyl ether (2-Nitro phenyl octyl ether) 92.4%;
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat once, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane 4 after volatilizing fully;
6) heat-shrink tube 5 is coated on tinsel 1 middle part and be part 0.5 centimetre away from ammonium ion sensitive membrane 4 ends more than.
1) with length be 8 centimetres tinsel 1, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 2M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) take by weighing respectively 10.1388g hydrochloric acid, 9.313g aniline, in the 100ml volumetric flask, add water to the solution that scale namely gets hydrochloric acid: aniline=1M:1M; Electroplate one deck electrically conductive polyaniline 2 with cyclic voltammetry on the top layer of tinsel 1 by the CHI760D electrochemical workstation;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel 1 is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) take by weighing 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 1:1), be dissolved in and be mixed with saturated solution among the 10mlDMF, the electrode that is coated with electrically conductive polyaniline 2 with the surface dips rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, oven dry is 4 hours in 150 ℃ of baking ovens;
4) ammonium ion carrier and attached component thereof are dissolved among the DMF according to forming A, are mixed with mixed solution, its composition A is by percentage to the quality:
Ammonium ion carrier (Ammonium ionophore I) 6.9%,
Four (4-chlorphenyl) potassium borate (Potassium tetrakis (4-chlorophenyl) borate) 0.7%,
2-nitrobenzene octyl ether (2-Nitro phenyl octyl ether) 92.4%;
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat once, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane 4 after volatilizing fully;
6) heat-shrink tube 5 is coated on tinsel 1 middle part and be part 1 centimetre away from ammonium ion sensitive membrane 4 ends more than.
1) with length be 10 centimetres tinsel 1, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) take by weighing 0.9720g commodity aniline hydrochloride chip solid, be dissolved in the 15ml deionized water, make the aniline hydrochloride solution of 0.5M; Electroplate one deck electrically conductive polyaniline 2 with cyclic voltammetry on the top layer of tinsel 1 by the CHI760D electrochemical workstation;
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel 1 is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) take by weighing 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 5:1), be dissolved in and be mixed with saturated solution among the 10mlDMF, the electrode that is coated with electrically conductive polyaniline 2 with the surface dips rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, oven dry is 4 hours in 150 ℃ of baking ovens;
4) ammonium ion carrier and attached component thereof are dissolved among the DMF according to forming B, are mixed with mixed solution, its composition B is by percentage to the quality:
Ammonium ion carrier (Ammonium ionophore I) 0.2%,
2-nitrobenzene octyl ether (2-Nitro phenyl octyl ether) 69.00%,
PVC（Poly(vinyl chloride) high molecular weight）30.80% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat 2 times, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane 4 after volatilizing fully;
6) heat-shrink tube 5 is coated on tinsel 1 middle part and be part 0.5 centimetre away from ammonium ion sensitive membrane 4 ends more than.
1) with length be 15 centimetres tinsel 1, surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) take by weighing 1.9439g commodity aniline hydrochloride chip solid, be dissolved in 15ml without in the ammonium water, make the aniline hydrochloride solution of 1M; Electroplate one deck electrically conductive polyaniline 2 with cyclic voltammetry on the top layer of tinsel 1 by the CHI760D electrochemical workstation.
Experiment parameter is: scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel 1 is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 1M, continuous sweep 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) take by weighing 35 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline (mol ratio of the two is 1:5), be dissolved in and be mixed with saturated solution among the 10mlDMF, the electrode that is coated with electrically conductive polyaniline 2 with the surface dips rapidly the DMF saturated solution of soluble polyaniline, be inserted in the crucible that fills sand, oven dry is 4 hours in 150 ℃ of baking ovens;
4) ammonium ion carrier and attached component thereof are dissolved among the DMF according to forming C, are mixed with mixed solution, its composition C is by percentage to the quality:
Ammonium ion carrier (Ammonium ionophore I) 1.00%,
Di-n-octyl sebacate (DOS) (Bis (2-ethylhexyl) sebacate) 66.80%,
PVC（Poly(vinyl chloride) high molecular weight）32.20% ；
5) dip fast mixed solution with the surperficial electrode that is coated with soluble polyaniline 3, repeat once, be inserted on the polyfoam, placed the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane 4 after volatilizing fully;
6) heat-shrink tube 5 is coated on tinsel 1 middle part and be part 0.5 centimetre away from ammonium ion sensitive membrane 4 ends more than.
The demarcation of solid ammonium ion-selective electrode:
The used mother liquor of preparation ammonium ion standard solution is the 0.1M ammonium ion standard solution (09683) that Sigma company produces, used thinning agent is for making by oneself without ammonium water, preparation method without ammonium water is as follows: distilled water by a storng-acid cation exchange resin (Hydrogen) post, is collected efflux with the vial with ground glass stopper.Add the same resin of 10g during storage in every up-flow fluid.(with reference to GB: GB/T-26812-2011)
Pipette 10ml10
-1The commercial NH of M
4Cl solution is used without ammonium water and is diluted to 100ml, makes 10
-2The NH of M
4Cl solution, the dilution preparation 10 successively
-3M, 10
-4M, 10
-5M, 10
-6The NH of M
4Cl solution.
Select electrode as working electrode take the self-control ammonium ion, commodity Ag/AgCl electrode is contrast electrode, respectively working electrode and contrast electrode are connected to the CHI760D electrochemical workstation, the response electric signal from high concentration toward the low concentration sequentially determining, according to response signal intensity and concentration relationship mapping, the two linear relationship slope is between 55.5 ~ 58, and meeting can Si Tedinglv.
Claims (5)
1. solid ammonium ion electrode based on electrically conductive polyaniline, it is characterized in that comprising tinsel (1), electrically conductive polyaniline (2), fusible conductive polyaniline (3), ammonium ion sensitive membrane (4), heat-shrink tube (5), tinsel (1) lower surface is electroplated one deck electrically conductive polyaniline (2), outside surface at electrically conductive polyaniline (2) coats one deck fusible conductive polyaniline (3), outside surface at fusible conductive polyaniline (3) is coated with again ammonium ion sensitive membrane (4), is coated with heat-shrink tube (5) in the part outside end 0.5-1 centimetre away from ammonium ion sensitive membrane (4) more than in the middle part of the tinsel (1) and be.
2. a kind of solid ammonium ion electrode based on electrically conductive polyaniline according to claim 1 is characterized in that, described tinsel (1) is Ag, Au, Pt, or the surface is coated with copper wire or the nickel wire of Ag, Au, Pt metal film.
3. a kind of solid ammonium ion electrode based on electrically conductive polyaniline according to claim 1 is characterized in that, described electrically conductive polyaniline (2) be tinsel (1) in the hydrochloric acid solution of aniline monomer, electroplate to form.
4. a kind of solid ammonium ion electrode based on electrically conductive polyaniline according to claim 1 is characterized in that, described fusible conductive polyaniline (3) is that mol ratio is the aniline of 1:5～5:1 and the doped hydrochloride multipolymer of 2.5-dimethoxyaniline.
5. preparation method based on the solid ammonium ion electrode of electrically conductive polyaniline is characterized in that its step is as follows:
1) with length be 5～15 centimetres tinsel (1), surface and oil contaminant is removed in first ultrasonic cleaning in acetone soln, and oxide is removed in ultrasonic cleaning in 1～2M watery hydrochloric acid again, uses without dry after the ultrasonic cleaning of ammonium water again;
2) aniline and hydrochloric acid are mixed with the aniline hydrochloride solution of 0.5～1M by the mol ratio of 1:1, perhaps with the aniline hydrochloride chip solid, are dissolved in without in the ammonium water, make the aniline hydrochloride solution of 0.5～1M; Electroplate one deck electrically conductive polyaniline (2) with cyclic voltammetry on the top layer of tinsel (1) by the CHI760D electrochemical workstation; Wherein, scanning current potential 0-0.45V, sweep velocity 50mV/s, sampling interval 1mV, sensitivity 10
-4A/V; Tinsel (1) is done anode, and auxiliary electrode is the Pt electrode, and contrast electrode is commercial Ag/AgCl electrode; Three electrodes are inserted simultaneously in the aniline hydrochloride solution of 0.5～1M, continuous sweep 10 ~ 20 circulations, with anhydrous alcohol drip washing electrode, stand-by after the alcohol volatilization after plating is finished;
3) get 5 to 50 milligrams of aniline and 2, the doped hydrochloride multipolymer of 5-dimethoxyaniline, with N, dinethylformamide is that solvent is mixed with saturated solution, dip rapidly the N of soluble polyaniline with the electrode that is coated with electrically conductive polyaniline (2), the dinethylformamide saturated solution is inserted in the crucible that fills sand, dries 4～6 hours in 80～150 ℃ of baking ovens;
4) the ammonium ion carrier I of Sigma company and film forming agent, plastifier, negative ion impedance agent are dissolved in the DMF, are mixed with mixed solution, its composition is respectively by percentage to the quality:
Form A:
Ammonium ion carrier I 6.9%;
Four (4-chlorphenyl) potassium borate 0.7%;
2-nitrobenzene octyl ether 92.4%;
Form B:
Ammonium ion carrier I 0.2%;
2-nitrobenzene octyl ether 69.00%;
PVC 30.80% ；
Form C:
Ammonium ion carrier I 1.00%;
Di-n-octyl sebacate 66.80%;
PVC 32.20% ；
5) electrode that is coated with soluble polyaniline (3) with the surface dips mixed solution 1～3 time, is inserted on the polyfoam, places the vacuum dryer vacuum drying 24 hours, until solvent obtains ammonium ion sensitive membrane (4) after volatilizing fully;
6) heat-shrink tube (5) is coated on tinsel (1) middle part and be part 0.5～1 centimetre away from ammonium ion sensitive membrane (4) end more than.
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| CN106093161B (en) * | 2016-06-02 | 2018-07-03 | 浙江大学 | Polyphenyl diamines is adulterated as ammonium ion electrode of sensitive membrane and preparation method thereof using proton |
| CN109507265A (en) * | 2019-01-08 | 2019-03-22 | 武汉新烽光电股份有限公司 | Throw-in type ammonia nitrogen water quality sensor |
| CN113564655A (en) * | 2021-07-15 | 2021-10-29 | 浙江大学 | Ammonium ion detection electrode for electrodepositing polyaniline-polystyrene sulfonic acid, preparation method and application |
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| CN106093161B (en) * | 2016-06-02 | 2018-07-03 | 浙江大学 | Polyphenyl diamines is adulterated as ammonium ion electrode of sensitive membrane and preparation method thereof using proton |
| CN109507265A (en) * | 2019-01-08 | 2019-03-22 | 武汉新烽光电股份有限公司 | Throw-in type ammonia nitrogen water quality sensor |
| CN113564655A (en) * | 2021-07-15 | 2021-10-29 | 浙江大学 | Ammonium ion detection electrode for electrodepositing polyaniline-polystyrene sulfonic acid, preparation method and application |
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